Catalysts for

METHANOL
SYNTHESIS
Catalysts for
Methanol Synthesis
INTRODUCTION

Catalysts
Clariant is a globally active specialty chemicals company, based in Muttenz,
Switzerland.

Our strength in methanol technology grows from our roots in Süd-Chemie, a

leading company in the development of process catalysts for chemicals mar-
kets. The broad portfolio of highly innovative catalyst products is now part of
the Catalysts business unit of Clariant.

The Catalysts Business Unit is headquartered in Munich, Germany, and has 16

production sites and 11 R&D centers around the world. Our catalysts contribute
significantly to value creation in our customers’ operations, ensuring that finite
raw materials and energy are used efficiently in the production of industrial
chemicals, plastics, and fuels. Our products enable the use of alternative raw
materials – such as natural gas, coal and biomass – as chemical and energy
feedstocks, and are used to clean emissions from industrial processes and com-
bustion engines to limit the impact on the environment.

We are committed to R&D and customer service to ensure that our products are
well positioned to meet the global challenges of raw material scarcity, energy
efficiency and responsible care for our environment.

2

AT THE EUROPEAN
CATALYST CENTER
The Heufeld site has
both catalyst produc-
tion and R&D.

3
Catalysts for
Methanol Synthesis
APPLICATION
Reactions
MegaMax® 800 catalyst is the next generation of methanol synthe-
sis catalyst, with much higher activity and selectivity than previ-
ous catalysts. This catalyst is utilized for methanol synthesis from
carbon monoxide, carbon dioxide and hydrogen.
CO + 2H2 ↔ CH3OH ∆HR = -91 kJ/mol
CO2 + 3H2 ↔ CH3OH + H2O ∆HR = -49 kJ/mol
Both methanol forming reactions are inter-connected with the
water gas shift reaction:
CO + H2O ↔ CO2 + H2 ∆HR = -42 kJ/mol
The above equilibrium reactions are exothermic, so low reaction
temperatures and high reaction pressures favor methanol yield.
Figure 1 shows an equilibrium curve for methanol as a function of
temperature and pressure.
4
Processes
Historically, methanol was produced at very high pressure – more
than 300 bar. Catalyst development during the late 1960’s and early
1970’s enabled the process to be carried out at much lower pres-
sures, from 40 to 100 bar (low pressure methanol process).
Today, industrial scale methanol synthesis is conducted either in
isothermal or in adiabatic converters utilizing indirect or direct
cooling. The main advantages of the low pressure process are:
· Lower investment and production costs
· Improved operational reliability and
· Much greater flexibility in the plant size
Older plant capacities ranged from 150 to 1,000 mtpd, while most
modern plants have an average production capacity of 2,000 to
2,700 mtpd. Lurgi introduced MegaMethanol® plants in recent
years, offering production capacities of 5,000 mtpd and higher in
a single train. And its latest development, GigaMethanol®, enables
production of up to 10,000 mtpd and is based on the high activity of
MegaMax 800.
Feedstock
The hydrocarbon feedstocks used to produce methanol are:
· Natural Gas
· LPG
· Naphtha
· Residual Oils
· Coal, and
· Off-Gases.

These feedstocks can be processed by several routes – Steam

Reforming, Partial Oxidation, and Gasification – to provide the
required carbon oxides for the methanol synthesis. Figure 2 shows
a typical flow sheet of the methanol synthesis loop design.

FIGURE 1 Methanol
Equilibrium Chart

FIGURE 2 Flow sheet of
the Methanol Synthesis
Process Design

Methanol [Vol%] Saturated Steam

30.0 Cooler
Separator
Steam Drum
Interchanger BFW
25.0

HP Steam
20.0

Recycle Gas
15.0 Compressor

50 bar Synthesis Gas

10.0 Compressor
Product Final
80 bar Separator Cooler
Methanol
120 bar Reactor
5.0 300 bar Synthesis Gas

LP Steam
Sea Water
0.0
100 150 200 250 300 350
Temperature [°C] Purge Gas Crude Methanol Blow Down

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Catalysts for
Methanol Synthesis
PRODUCT FEATURES

Performance MegaMax 800 boosts productivity of older units and delivers the
Clariant has studied Cu/Zn/Al chemistry in catalytic processes performance that you have come to expect from MegaMax prod-
for many years, with internal R&D programs and with external ucts, including:
universities. The first result of these collaborative activities was · High activity,
MegaMax 700, which offered improved activity, selectivity and · High physical strength,
poison resistance over previous catalysts. MegaMax 800 is the · High selectivity,
next generation methanol synthesis catalyst, proving even higher · Low temperature activity,
activity than previous generations and alternative catalysts on the · Low pressure drop,
markets. · Poison tolerance, and
· Longevity.
MegaMax 800 builds on our wealth of experience in the methanol
and syngas markets. This catalyst offers the flexibility to run in The typical operating conditions for methanol production using
large and small production units, and with a variety of production MegaMax 800 are:
technologies. Temperature: 190 - 315 °C, and
Pressure: 20 - 125 bar g.

Table 1 gives an overview of MegaMax 800 chemical composition

and typical physical properties.

TABLE 1 Chemical Composition and Physical Properties of MegaMax 800

Composition copper oxide, zinc oxide, alumina

Size and Shape 6 x 4 mm Tablets, 6 x 5 mm Tablets
Bulk Density 1.2 kg/l
Side Crush Strength 210 N

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FIGURE 3 Activity
Comparison MegaMax
Series Catalysts

FIGURE 4 Predicted
Performance of
MegaMax 800

Activity Relative Activity [%]

Optimal catalyst activity depends on the delicate balance between 140
copper surface area, the number of active copper sites and copper
crystallite size. The ideal formulation exhibits an extremely stable 130
matrix with the optimum number of small copper crystals. To
achieve long-term performance, it is also important to maintain 120

this energy-rich state as long as possible, which means ensuring

that sintering is suppressed as far as possible. These properties may 110 MegaMax® 800

be realized through a combination of catalyst precursors, catalyst MegaMax® 700

composition and catalyst manufacturing techniques. By utilizing 100
Benchmark
the latest research and applying state-of-the-art production tech-
nologies, Clariant has succeeded in: 90
0 50 100 150 200 300
· increasing copper surface area, Time on Stream [hours]
· improving copper dispersion,
· decreasing copper crystallite size, and
· improving pore structure (pore volume and pore size distribution) Carbon Efficiency [%]
100
The novel MegaMax 700 methanol synthesis catalyst provided at
least a 20% higher level of initial activity compared to a Benchmark
95
synthesis catalyst, and MegaMax 800 offers a 35 - 40% boost over
Benchmark (Figure 3).
90

The extremely high activity and productivity of the MegaMax MegaMax® 800
Series catalysts allows new methanol plant designs, such as a
85
MegaMethanol® plant (Lurgi), to operate using lower catalyst Benchmark

volumes per ton of methanol, while providing for high carbon

and energy efficiency, all of which results in lower cost methanol 80
0 11250 22500 33750 45000
production. And the high activity of MegaMax 800 has enabled the Cumulative Methanol Production [mt/m3]
development of GigaMethanol, which allows production of up to
10,000 mtpd.

Because of its high stability, MegaMax 800 will maintain its high
activity level for a lifespan as long as five years, with an expected
cumulative methanol production of 45,000 metric tons per cubic
meter of catalyst (Figure 4).

7
Catalysts for
Methanol Synthesis
MEGAMAX

Selectivity
The process conditions that influence selectivity are:
· Reaction temperature,
· CO2 concentration at reactor inlet,
· Operating pressure, and
· H2 /CO ratio in make-up gas.

By far the most important factors are temperature and CO2 concen-
tration inlet the reactor. An increase in reaction temperature leads
to a significant increase of by-product formation, but high CO2 con-
centrations in the feed significantly reduce the by-product forma-
tion. Additionally, catalyst formulation also influences by-product
formation.

In principal, the production of methanol and the formation of

undesired by-products such as higher alcohols, esters, ethers and
ketones occur through the same intermediate species on the active
copper site of the catalyst. Therefore, with conventional catalysts,
an increase in catalytic activity for methanol formation will also
lead to increased by-product formation.

Our extensive research and development work established manu-

facturing techniques that produced a catalyst with a much higher
activity level that also exhibited superior selectivity compared to
existing catalysts. Consequently by-product formation over the en-
tire life of MegaMax 800 is very low compared to existing catalysts.

Although by-product formation increases with time-on-stream as

the reaction temperature is raised to compensate for activity decay,
the extremely high selectivity of MegaMax 800 is maintained and
outperforms that of Benchmark.

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Mechanical Stability
The physical and mechanical properties of methanol synthesis cat-
alysts have a significant impact on performance and longevity. The
catalyst must be physically strong enough to withstand the abuse
of the initial loading procedure, routine operation and potential
process upsets. A mechanical breakdown of the catalyst pellet could
result in an unacceptably high pressure drop and/or gas channel-
ing, leading to a decreased methanol formation rate and ultimately
the need for premature replacement.

Figure 5 illustrates typical side crush strengths of the MegaMax 800

catalyst compared to MegaMax 700 and a benchmark methanol
synthesis catalyst. Note that MegaMax 800 shows an additional
15% improvement in crush strength over the excellent performance
of MegaMax 700.

The extremely high crush strength of the catalyst in the oxide form
allows easy handling, transportation and loading. Screening or siev- FIGURE 5 Side Crush
ing the catalyst prior to loading is usually not necessary. Strength of
MegaMax 800

The exceptional retention of catalyst strength after catalyst re-

Relative Side Crush Strength [%]
duction is important to provide the necessary endurance for daily
160
operation and protection against process upsets.
140

Catalyst Activation 120

The MegaMax 800 catalyst is shipped in the oxide state and is easy 100
to commission. For details please refer to the Operating Manual for 80
MegaMax 800. Additionally, the Catalysts business is always pre- MegaMax® 800
60
pared to provide a technical expert to review procedures and assist
MegaMax® 700
with start up, and a self-contained hydrogen analyzer is available 40

for tight control of reduction conditions. Our service will help to 20 Benchmark

keep down-times short and assure a trouble-free start-up as far as 0

possible. Catalyst

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Catalysts for
Methanol Synthesis
MEGAMAX
Experience
Clariant has developed a series of methanol synthesis catalysts
that have successfully operated in the widest possible spectrum of
operating conditions and in a variety of reactor designs. Also the
capacities of units using MegaMax vary widely from 50 tons per
day to 10,000 tons per day.
Makeup Gas
The makeup gas analysis composition depends on the synthesis
gas generation technology. Makeup gas can be characterized by its
stoichiometric number. The stoichiometric number is defined as
SN = (H2 - CO2 ) / (CO + CO2 )
Steam Methane Reforming (SMR)
Most of the worlds methanol production is based on synthesis gas
generated from steam reforming of either natural gas (Table 2)
or naphtha. Depending on the reforming process, there is a wide
variety of makeup gas compositions with varying stoichiometric
numbers. CO2 can be added to adjust the SN of a steam reforming
process gas. The addition of CO2 decreases the by-product forma-
tion across the catalyst and the amount of make-up gas needed per
ton of production due to a better stoichiometric number. The make-
up gas produced by the Lurgi combined reforming process (tubular
steam methane reformer combined with oxygen blown autothermal
reformer) results directly in the optimum SN of 2.05. Typical syn-
thesis gas compositions from steam reforming are shown in Table 3.
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Partial Oxidation (POX)
Partial oxidation of natural gas, heavy residual oil or coal results in
a makeup gas that is very rich in CO, but contains little CO2 and in-
erts. It is necessary to treat such a process gas with CO shift conver-
sion followed by CO2 removal and a sophisticated cleanup system to
adjust the stoichiometric number and to remove the relatively high
amounts of sulfur and heavy metals in the feedstock.
Independent of the loop design, the make-up gas composition
determines the specific makeup gas consumption. Makeup gas
consumption is defined as the kg-moles of makeup gas per metric
ton of methanol in the crude methanol and is a measure of the plant
efficiency, which also effects by-product formation in the loop.
The lowest specific makeup gas consumption is obtained with the
optimum SN = 2.05, and the lowest inert level in the synthesis gas,
i.e. using gasification gas (Table 4). The highest specific makeup
gas consumption usually results in the case of steam reforming of
natural gas without CO2 addition. Such a synthesis gas is hydrogen
rich with SN close to 3.0, which is quite high for efficient methanol
production.
 SMR WITHOUT SMR WITH LURGI
CO2 ADDITION CO2 ADDITION COMBINED
REFORMING

[vol%]
CO 14.2 14.6 20.6
CO2 8.5 12.7 8.5
H2 72.7 70.6 70.6
CH4 4.3 1.9 2.2
N2 + Ar 0.3 0.2 0.2
Stoichiometric 2.8 2.1 2.05
Number

MAKEUP GAS REACTOR INLET

[vol%]
CO 29.0 10.6
CO2 2.4 3.5

H2 69.9 73.0
TABLE 2 Typical CH4 0.3 5.0
Compositions of
Synthesis Gas from N2 + Ar 0.4 7.9
Steam Reforming Stoichiometric Number 2.15 4.93

TABLE 3 Typical
Compositions of SPECIFIC MAKEUP GAS CONSUMPTION [kmole/mt]
Partial Oxidation Gas
Gasification (residual oil) 95 - 105

Combined Reforming 110 - 120
TABLE 4 Specific
Makeup Gas Consump- Steam Reforming with CO2 Addition 120 - 130
tion for different
Synthesis Gas Processes Steam Reforming without CO2 Addition 140 - 150

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Catalysts for
Methanol Synthesis
MEGAMAX

Reactor Designs
Methanol synthesis reactors feature adiabatic multi-bed quench or
indirect cooled converters, isothermal steam raising tubular reac-
tors and tube (gas) cooled designs. MegaMax catalyst can be used
in all of these reactor types.

Clariant developed computer models to simulate all of the follow-

ing reactor designs on the basis of rate equations derived from the
MegaMax series of methanol synthesis catalysts. These models are
described in the Operating Manual for MegaMax 800.

Isothermal Reactor
There are five different types of isothermal reactor designs:
1. LURGI tubular steam raising reactor with the catalyst in the
tubes and boiling water on the shell side. The heat of reaction is
utilized to produce process steam. (Figure 6)
2. Casale isothermal methanol converter that is either gas-cooled
or steam-raising.
3. TOYO MRF-Z steam raising reactor with radial process gas flow
mode.
4. LINDE steam raising spiral reactor with the catalyst on the shell
side and steam produced inside the coils, which are built in spi-
rals through the catalyst bed.
5. ICI tube cooled converter with the catalyst on the shell side and
straight cooling tubes inside the catalyst bed.

Adiabatic Reactor
FIGURE 6 Lurgi
There are two different types of adiabatic reactor designs: Isothermal Reactor
1. multi-bed quench (direct cooling) in Iozenge (Figure 7), ARC or
CMD design, and FIGURE 7 ICI lozenge
2. multi-bed with inter-stage heat exchange (indirect cooling). reactor

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Operational Parameters IMPURITIES [ppm wt.]
In commercial plants, there is normally a fixed feedstock, makeup
Ethanol 121
gas composition and loop design. With all designs, the general rule
Total Higher Alcohols 342
is to always operate the methanol synthesis catalyst with the lowest
reaction temperature possible, while maintaining the desired meth- Acetone 1

anol production rate and quality. MEK 3

Total Ketones 6
The inherent loss in activity of any methanol synthesis catalyst over Grand Total 568
time in service can be compensated for by the following operating
parameters:
· reaction temperature, TABLE 5 Typical
· quench gas distribution, By-Products in
Crude Methanol
· operating pressure,
· recycle ratio (not possible with every design), and
· purge rate.

By-Products
In principle, the by-products formed during methanol synthesis
are compounds such as higher alcohols, esters, ethers and ketones.
Ketones and acetone are critical by-products in terms of achieving
Grade AA methanol product.

As an example of the selectivity of MegaMax 800 catalyst, Table 5

lists typical levels of by-products in large scale industrial methanol
plants (conditions: combined reforming, operating pressure = 80
bar g, steam jacket temperature = 232 °C).

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Catalysts for
Methanol Synthesis
MEGAMAX
Poisons
MegaMax 800 methanol synthesis catalyst is a copper-based
catalyst so any constituent in the feed gas that reacts with copper
acts as a poison. The primary deactivation mechanism for methanol
synthesis catalysts is poisoning by trace levels of sulfur and chlo-
rides in the feed gas.
To a lesser extent, the catalyst is also deactivated by thermal sin-
tering of the copper crystals. Sintering results in the formation of
larger copper crystallites with a corresponding reduction in copper
surface area. In addition, solid particles such as dust in the feed
and trace metals physically block the catalyst surface and lead to
premature deactivation of the catalyst.
Sulfur – As with all copper based catalysts, the MegaMax 800 cata-
lyst is deactivated by sulfur. The sulfur content in the synthesis gas
(or nitrogen circulation) should be less than 0.05 ppm v as H2S. A
sulfur content of more than 0.8 wt% on the catalyst, deactivates the
catalyst completely.
Iron – If iron in the form of iron carbonyls is carried onto the meth-
anol synthesis catalyst, this catalyzes the Fischer-Tropsch reaction
and consequently by-product formation increases. Iron and other
heavy metals also block the active sites of the catalyst, thus reduc-
ing activity. Nickel has a similar deleterious effect on the catalyst
performance.
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Chlorine/Chlorides – Chlorine in any form, e.g. Cl2, HCl or R-Cl, is
a strong poison to the methanol synthesis catalyst. Copper chloride
sinters quickly, which reduces the active copper surface area of the
catalyst. Chlorine should be excluded completely from the system;
chlorine content in the synthesis gas should be at a non-detectable
level. Chlorides more than 500 ppm wt on the catalyst deactivates
the catalyst completely.
Oil – Any carry-over of lubricating oil should be avoided as it is well
known that these heavy hydrocarbons have a deactivating effect on
methanol synthesis catalysts.
Steam – Steaming of methanol synthesis catalyst must be avoided as
it leads to an accelerated growth of copper crystals and deactivates
the catalyst prematurely.
Oxygen – Oxygen can also be considered a poison as oxygen contact
with the reduced catalyst leads to partial re-oxidation followed by
subsequent reduction by the process gas. These redox reactions af-
fect the structure of the catalyst and lead to premature loss in crush
strength and a rapid increase in pressure drop a rapid decrease in
pressure. This can also lead to thermal sintering with a consequen-
tial loss in active copper surface area.
Sales and Technical Services
The Catalysts business offers its customers complete service
regarding to the use of any of the catalysts it supplies. This service
begins with supplying process information to the engineering
contractor or the customer during the initial stages of design and
construction of a plant; continues through start-up services when
the plant is placed online; and subsequent follow-up service to
assist the customer in maintaining optimum operating performance
of the catalysts. This service is available to the customer throughout
the life of the catalyst.

Our Technical Services Group offers a wide range of personnel with

specific expertise in the areas of catalyst characterization, research,
catalyst installation, start-up, plant operation and performance
evaluations.

This in-depth knowledge allows us to provide the following services:

· Review of reactor system design
· Selection of proper catalysts
· Technical reviews of start-up/shut-down procedures
· Technical assistance for loading catalyst upon start-up and
shut-down
· Routine performance evaluations
· Troubleshooting
· Catalyst life-projections
· On-site training seminars for engineering and operations personnel
· Chemical and physical analyses of spent catalyst
· Supply proprietary computer programs for catalyst performance
evaluation

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Rothausstrasse 61
4132 Muttenz
Switzerland

CATALYSTS
syngas@clariant.com

CLARIANT.COM/CATALYSTS

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